Photographic water-insoluble compounds having a hydrophobic diffusion-fast substituent

ABSTRACT

Photographic materials are described which comprise in a lightsensitive silver halide emulsion layer or in another waterpermeable colloid layer a non-diffusing water-insoluble photographic component containing a hydrophobic diffusion-fast making group of the formula   WHEREIN X is an ether group, a thioether group, a sulphonyl group, CONH, NHCO or SO2NH and each of R1 and R2 is a branchedchain C4-C12 alkyl group. The described materials comprise the said component in the form of a finely divided dispersion which shows no crystallization tendency.

Van Poucke et al.

[ PHOTOGRAPHIC WATER-INSOLUBLE COMPOUNDS HAVING A HYDROPHOBICDIFFUSION-FAST SUBSTITUENT [75] Inventors: Rapha'e'l Karel Van Poucke,

Berchem; Arthur Henri De Cat, Mortsel, both of Belgium [73] Assignee:Agfa-Gevaert N.V., Mortsel,

Belgium [22] Filed: Feb. 8, 1971 [21] App]. No.: 113,646

[30] Foreign Application Priority Data Feb. 24, 1970 United Kingdom...;8840/70 [52] US. Cl. 96/100; 96/l09; 96/55 [51] Int. Cl G03c 1/40 [58]Field of Search 96/55, 100, 95

[56] References Cited UNITED STATES PATENTS 3,005,709 lO/1961 Coles96/100 3,409,439 11/1968 Yoshida 96/100 3,658,545 4/1972 lwama 96/1003,676,141 7/1972 Hara 96/100 14 1 -July 1, 1975 3,692,527 11/1972 Konig96/100 Primary Examiner-Norman G. Torchin Assistant Examiner.lohn L.Goodrow Attorney, Agent, or Firm-A. W. Breiner [57] ABSTRACTPhotographic materials are described which comprise in a light-sensitivesilver halide emulsion layer or in another water-permeable colloid layera non-diffusing water-insoluble photographic component containing ahydrophobic diffusion-fast making group of the formula wherein X is anether group, a thioether group, a sulphonyl group, CONl-l, Nl-lCO or SONl-l and each of R and R is a branched-chain C C, alkyl group. Thedescribed materials comprise the said component in the form of a finelydivided dispersion which shows no crystallization tendency.

12 Claims, No Drawings 1 PHOTOGRAPHIC WATER-INSOLUBLE COMPOUNDS HAVING AHYDROPI-IOBIC DIFFUSION-FAST SUBSTITUENT This invention relates towater-insoluble photographic components containing branched-chainhydrophobic groups rendering said components fast to diffusion inphotographic hydrophilic colloid media and to photographic elementscontaining such components.

In the preparation of photographic silver halide emulsion layers andother hydrophilic colloid layers of a photographic silver halidematerial it is often necessary to incorporate therein components such ascolour couplers, mask-formers, competing couplers, U.V.- absorbers, etc.that are non-diffusible in these hydrophilic colloid media so that theydo not wander from their original site. For this purpose the saidcomponents are usually provided in their molecule with one or moreballast groups e.g. a long chain aliphatic group such as an alkyl groupcontaining from 5 to '20 C-atoms in straight line. This ballast groupimparts to the molecule a hydrophobic character and holds the componentfirmly in the original hydrophilic colloid layer.

The methods according to which these non-diffusing components areincorporated into the photographic hydrophilic colloid layers presentnumerous problems and much effort has been directed to solve theseproblems.

A method commonly employed to incorporate these non-diffusing componentsinto hydrophilic colloid compositions such as a gelatino silver halideemulsion is to provide in. the molecule of said components one or moresalt-forming groups ie carboxy and/or sulpho groups so that they can bedissolved in the hydrophilic colloid composition in the form of theirsoluble alkali metal salts.

The incorporation of these non-diffusible components containingsalt-forming groups into aqueous hydrophilic colloid compositionsfrequently poses a number of difficulties. Indeed, many of thesecomponents carrying sulpho and/or carboxyl groups are not solubleenough, i.e. in the concentration desired, in said alkaline solutionswhile others crystallize after some time in said solutions or give riseto flocculation when incorporating the ingredient solution in theaqueous hydrophilic colloid medium. Moreover, some compounds are solubleonly in highly alkaline solutions which are too basic for use as such inconventional light-sensitive silver halide material, where approximatelyneutral solutions are most desirable; when highly alkaline solutions areused the hydrophilic colloid composition should be reacidifiedafterwards whereby flocculation might occur and whereby inorganic saltsare formed. Another problem accompanying the use of these components isdue to the presence of the water-solubilizing groups, especially thesulpho groups. Indeed, these groups have a marked influence on theviscosity of the hydrophilic colloid medium e.g. it is difficult toobtain, under the same circumstances, reproducible viscosity values forhydrophilic colloid compositions comprising suchlike components and onstoring such compositions the viscosity undergoes further changes.

Alternate processes of incorporating non-difi'using components inphotographic colloids make use of dispersion techniques.

According to one such method, e.g. as described in German PatentSpecification No. 1,127,714, waterinsoluble colour couplers aredissolved in low-boiling substantially water-immiscible solvents such asethyl acetate, methylene chloride, chloroform, etc. whereupon thesolution formed is dispersed in extremely: fine droplets in the presenceof a wetting or dispersing agent into the hydrophilic colloid mediumafter which the solvent is removed by evaporation, leaving behind adispersion of colour coupler distributed throughout the hydrophiliccolloid composition.

Another process for dispersing non-diffusing components in photographichydrophilic colloid compositions is described in US. Pat. No. 2,322,027.According to this method a colour coupler is dissolved in a highboilingoily solvent such as tricresyl phosphate and din-butyl phthalatewhereupon the resulting solution is dispersed in the form of extremelyfine droplets in the hydrophilic colloid composition, the oily solventbeing left in the said composition.

One of the advantages of these dispersion techniques is that componentsmay be used which contain no saltforming groups. However, theseprocesses also pose difficulties. Indeed, components that are intendedto be incorporated into photographic colloid media from solutions inlow-boiling or high-boiling organic solvents should have a sufficientsolubility in said solvents and be homogeneously distributed through thesaid colloid media before as well as after coating to form a hydrophiliccolloid layer of a photographic material so that no crystallization ofthe component occurs.

This condition limits the number of components suitable for suchapplications. Various components having one or more ballast groups ofhydrophobic character are not sufficiently soluble in said organic lowor high boiling solvents or give rise to crystallization of thecomponent either when dispersing the organic solution into thehydrophilic colloid medium, or when coating the hydrophilic colloidmedium to form a layer of a photographic material or when processing thephotographic material. In this way the degree of dispersion is markedlydecreased and as a consequence has a disadvantageous effect on thesensitometric characteristics of the photographic material.

It has now been found that photographic waterinsoluble components, suchas colour couplers, maskformers, competing couplers, U.V.-absorbers,etc., not containing a hydrophilic group and comprising asdiffusion-fast making hydrophobic group a group of the formula wherein Xstands for O, S, S0 CONI-I, Nl-ICO or SO NI-I and each of R and R standsfor a branchedchain C,C alkyl group, are particularly suitable for beingdispersed into hydrophilic colloid media with the aid of high-boilingand/or low-boiling water-immiscible or sparingly water-miscible solventsin that their solubility in the said solvents is superior than thesolubility of the corresponding components having straight-chainballasting alkyl groups and that as compared with the latter componentsthey do not give rise to the above disadvantageous effects ofcrystallization. The above diffusion fast making group should behydrolytically stable in the processing solutions for the photographicmaterial and therefor not ester linked to the molecule of thephotographic component. 7

By colour coupler is meant any compound which in silver halidephotography couples with an oxidized aromatic primary amino colourdeveloping agent to form a dye image. Examples of such colour developingagents are p-phenylene diamine and derivatives thereof for exampleN,N-dialkyl-p-phenylene diamines such as N,N-diethyl-p-phenylenediamine, N,N-dialkyl-N- sulphomethyl-p-phenylene diamines andN,N-dialkyl- N-carboxymethyl-p-phenylene diamines, Z-amino-S-diethylamino-toluene. etc.

By mask-forming component there is meant a compound which oxidativelycouplers with a colour coupler in an oxidizing bleaching bath as forexample described in United Kingdom Patent Specification Nos. 880,862and 975,932 to form a coloured mask image.

Competing couplers are compounds which are used in conjunction withcolour couplers in silver halide colour photography and which couplewith the oxidized aromatic primary amino colour development agent toform colourless coupling products e.g. as described in United KingdomPatent Specification No. 861,138.

In the preparation of the photographic components according to thepresent invention inexpensive and easily available primarybranched-chain alcohols comprising at least 10 carbon atoms can be usedas starting materials for introducing the diffusion fast making group inthe photographic component molecule.

Examples of branched-chain alcohols that can be used are the widelyknown branched-chain primary oxo-alcohols having at least l C'atoms andwhich can be represented by the formula /R1 HOCH; CH

wherein R and R have the same significance as above, such asisodecylalcohol, isotridecylalcohol, isohexadecylalcohol andisooctadecylalcohol. Isodecylalcohol is a commercial material preparedfrom C olefins (tripropylene) by means of the oxo-synthesis (cf. H.Rompp Chemie Lexikon Francksche Verlag Stuttgart, W. Germany) and is amixture of primary branched-chain C r-alcohols. Isotridecylalcohol is acommercial material prepared from C -olefins (triisobutylene,tetrapropylene or di(2-methyl-l pentene) by means of the oxo-reactionand is a mixture of primary branched-chain C -alcohols.lsohexadecylalcohol and isooctadecylalcohol are commercial materialsprepared by aldol-condensation of C,,- or C aldehydes formed byoxo-synthesis, isohexadecylalcohol is a mixture of branched-chainprimary Cur-alcohols mainly consisting of alcohols as represented by theabove formula wherein R dimethylbutyl and R dimethylhexyl whereasisooctadecylalcohol is a branched-chain alcohol for which the followingformula is given:

on, CH3 CH3 CH3 H3C- -CH1( JH-CHCH;CH:HCH1 -CH;

(in, onion dHa More details regarding the composition, the preparationand the properties of branched-chain oxo-alcohols can be found inFortsch.Chem.Forsch. Bd ll/l p. l2l-134.

Other branched-chain alcohols which can be used as starting materialsare the branched-chain alcohols prepared by alkaline condensation, usingcatalytic amounts of alkali such as potassium hydroxide at tem- 5peratures comprised between 200 and 300C, (known as Guerbet-reaction seee.g. Fette-Seifen- Anstrichmittel, 71, no. 3, p. 2l5-2l8 (1969)) of abranched-chain alcohol with the same or other branched-chain alcohol.

The components according to the present invention can be represented bythe following general formula:

Ri Q XCHICH wherein:

X, R, and R have the same significance given above, and

Q stands for the residue of a photographic component that is to beincorporated in photographic hydrophilic colloid media in a form fast todiffusion, for example a colour coupler residue capable of forming a dyeimage on coupling with an oxidized aromatic primary amino colourdeveloping agent such as a'residue of a cyan-forming colour coupler ofthe phenol or naphthol type, of a magentaforming 'colourcoupler of thepyrazolone or indazolone type or of a yellow forming colour coupler ofthe acylacetamide especially the benzoylacetanilide type; a mask-formerresidue, a U.V.-absorber residueand 'a competing coupler residue. rlnaccordance with the present invention there is provided a photographicsilver halide material comprising in a silver halide emulsion layer orin a hydrophilic colloid layer of said material a water-insolublephotographic component comprising in its molecule a group rendering saidcomponent fast to diffusion in hydrophilic colloid media wherein saidgroup is a group of the above formula.

The following are representative examples of photographic componentshaving a branched-chain diffusion-fast making group as defined above inaccordance with the invention.

CsHn

The following preparations illustrate how these compounds can beprepared.

PREPARATION 1: COMPOUND l a. p-isohexadecylthio-chlorobenzene 14.5 g ofp-chlorothiophenol and 4 g of sodium hydroxide were dissolved in 200 mlof methanol, whereupon 30.5 g of isohexadecyl bromide prepared as knownby those skilled in the art of organic synthesis from isohexadecylalcohol (commercially available from Esso Belgium N.V., Antwerp,Belgium), and hydrobromic acid, were added and the whole was refluxedfor 5 hours. The reaction mixture was poured into 1 l of water and theoil formed was extracted with methylene chloride. After drying, overmagnesium sulphate and distillation under reduced pressure, 28 g ofp-isohexadecylthio-chlorobenzene were obtained.

Boiling point: l-165C/0.l5 mm. V b.p-isohexadecylsulphonyl-chlorobenzene A mixture of 36.9 g ofp-isohexadecylthiochlorobenzene, 180 ml of acetic acid and m] of dioxanwas heated to C whereupon 41 ml of 50% aqueous hydrogen peroxide wereadded in 1 hour. The mixture was stirred for l h on a boiling water bathand then cooled to room temperature. The oil formed upon pouring into400 ml of water was separated and the aqueous layer extracted withether. The ether layer was washed with a 10% solution of sodiumbisulphite, dried and concentrated.

Yield: 37 g. c. p-isohexadecylsulphonylphenylhydrazine 40 g ofp-isohexadecylsulphonyl-chlorobenzene in 70 ml of ethylene glycolmonomethyl ether and 41.6 ml of anhydrous hydrazine were refluxed for 60hours. Upon pouring the reaction mixture into 800 ml of water andextracting with benzene, 36 g of an oil comprising 92% ofp-isohexadecylsulphonyl-phenylhydrazine were obtained.

d. 1 -p-isohexadecylsulphonylphenyl-3-amino-2- pyrazolin-S-on 36 g ofthe above hydrazine, 20 g of B-amino-B- ethoxyacrylic acid ethyl ester,0.6 ml of acetic acid and 25 ml of acetonitril were heated for 2 hoursat 60C.

The acetonitrile was removed by evaporation and the residue was treatedwith a solution of 4.6 g of sodium in ml of methanol. The mixture waskept for 3 hours at 4045C whereupon 100 ml of water was added and themixture was acidified to pH 3 by means of 5 N hydrochloric acid. Theprecipitate formed was filtered off and recrystalized, after drying,from methano].

Yield: 20 g.

Melting point: 147C.

e. Compound 1 v 46 g of the above 2-pyrazolin-5-on and 20 g of anisidinehydrochloride were refluxed for 90 minutes in 80 ml of acetic acid. Themixture was poured into 800 ml of water whereupon the oil formed waspurified by dissolving in boiling acetonitrile.

Yield: 30 g.

Melting point: 40C.

PREPARATION 2: COMPOUND 2 a. p-isohexadecyloxy-benzoic acid 57.5 g ofsodium were dissolved in 2800 ml of ethylene glycol monomethyl etherwhereupon 380 g of phydroxy-benzoic acid methyl ester were added fol.-lowed by 762 g of isohexadecyl bromide. The reaction mixture wasrefluxed for 20 hours and then treated with 380 g of sodium hydroxide in1 l of water whereupon the mixture was again refluxed for 2 hours. Onelitre of concentrated hydrochloric acid was added and the mixture pouredinto l of water. The oil formed was separated and the aqueous layerextracted with methylene chloride. The organic layer and the methylenechloride extract were put together and washed with water. The mixturewas dried and'the solvent removed.

Yield: 694 g of an oil comprising 98% of pisohexadecyloxybenzoic acid.

b. p-isohexadecyloxy-benzoyl chloride 36.2 g ofp-isohexadecyloxy-benzoic acid and 35.7 g of thionyl chloride wererefluxed for 5 hours on a water bath whereupon the excess of thionylchloride was removed by evaporation. The residue was distilled at areduced pressure of 0.1 mm.

Yield: 33.5 g

Boiling point: 180C.

c. Compound 2 26.7 g of anhydrous aluminium chloride were dissolved in200 ml of pyridine. Once the exothermic reaction had come .to an end,30.7 g of 1-p-(l,l,2-. trifluoro-2-chloroethoxy)phenyl-3-amino-2-pyrazolin- 5-on prepared as described in BelgianPatent Specification 736,252 were added as well as 38 g ofpisohexadecyloxy-benzoylchloride. The mixture was stirred for 4 hours at80C whereupon it was concentrated by evaporation and the residuedissolved in 400 ml of ethylene glycol monomethyl ether. The mixture waspoured into 280 ml of concentrated hydrochloric acid and 800 g of ice.The precipitate formed was filtered and washed with water, whereupon itwas recrystallized from 400 ml of ethanol.

Yield: 35.5 g.

Melting point: 173C.

PREPARATION 3: COMPOUND 3 27 g of anhydrous aluminium chloride weredissolved in 200 ml of pyridine. To the solution formed were added 46.3g of 1-p-isohexadecylsulphonylphenyl-3- amino-2-pyrazolin-5-on and 17.6g of isononane carboxylic acid chloride prepared in the usual way fromthe corresponding carboxylic acid marketed by Novadel, Ltd., London. Themixture was stirred for 1 hour on a water bath whereupon it wasconcentrated by evaporation under reduced pressure and the residueformed was dissolved in boiling methanol. The mixture was acidified with280 ml of concentrated hydrochloric acid and the precipitate formed wasrecrystallized,

8 after having been washed with water, from 300 ml of ethanol.

Yield: 32 g. Melting point: 126C.

PREPARATION 4: COMPOUND 4 This compound was prepared in an analogous wayas compound 3 starting from 27.3 g of p-( 1,1,2-trifluoro-2-chloroethoxy)-benzoyl chloride (Bull.Soc.Chim.Fr. 1957, 821 Afterrecrystallization from ethanol, 40 g of colour coupler were obtained.

Melting point: 160C.

PREPARATION 5: COMPOUND 5 a. lsohexadecylthio-succinic anhydride Thiscompound was prepared by addition of isohexadecylmercaptan to maleinicanhydride in the presence of triethylene diamine according to the methoddescribed in Journal Organic Chemistry 27'; 3140-3146 (1962). Whenstarting from 130 g of isohexadecylmercaptan 100 g of a reddish brownoil were obtained.

Boiling point: 200C/0.5 mm.

b. Compound 5 2.2 g of S-amino-indazolone were dissolved .with heatingin 10 ml of acetic acid. 5.1 g of isohexadecylthio-succinic anhydridewere added whereupon the white precipitate formed was recrystallizedfrom acetonitrile.

Melting point: 162C.

PREPARATION 6: COMPOUND 6 a. o-isohexadecyloxy-nitrobenzene 260 g ofo-nitrophenol were dissolved in 1200 ml of dimethylformamide whereupon123 g of potassium hydroxide were added. 600 g of isohexadecyl bromidewere added whereupon the mixture was refluxed for 90 minutes. Themixture was poured into water and the oil formed extracted withmethylene chloride, whereupon the residue was distilled under a reducedpressure of 0.2 mm and a temperature of 180C.

Yield: 800 g.

b. oisohexadecyloxyani1ine 497 g of the above nitro compound weredissolved in 3 l of methanol and then reduced by catalytic hydrogenationusing Raney-nickel as catalyst at 80C and a hydrogen pressure of 1800psi. The Raney nickel was filtered off and the methanol removed byevaporation whereupon the residue was distilled under a reduced pressureof 0.2 mm at l55160C.

Yield: 400 g.

c. Compound 6 22.7 g of p-( 1,1 ,2-trifluoro-2-chloro-ethoxy)-benzoylacetic acid ethyl ester prepared as described in Belgian PatentSpecification 736,253 were condensed with 24 g ofo-isohexadecyloxyaniline in a medium of 53 ml of xylene, by removingduring 1 hour the alcohol formed during the condensation bydistillation. The oil formed was treated, after removal of the xylene,with 70 ml of water and 7 g of copper acetate. The copper chelate formedwas filtered off and washed with acetonitrile. The mixture was taken upin methylene chloride whereupon ml of 5N, hydrochloric acid were addedand then the organic layer was washed till neutral.

After removal of the solvent, 34 g of an oil were obtained. According tothin layer chromatography this oil did not comprise impurities. Thecontent of active methylene groups in the product obtained wasdetermined by titration with potassium methylate in dimethyl formamideas solvent and was found to be 100%.

PREPARATION 7: COMPOUND 7 a. o-isohexadecyloxy-acetophenone 600 g ofo-hydroxyacetophenone in 3 l of dimethyl formamide were treated with 252g of sodium methylate. The methanol formed was removed by evaporation ona boiling water bath at a reduced pressure of 20 mm. Then 1345 g ofisohexadecyl bromide were added and the mixture stirred for 6 hours on aboiling water bath. The reaction mixture was poured into 10 l of water,the organic layer was separated and the aqueous layer extracted withmethylene chloride. After removal of the solvent by evaporation, the oilwas treated in a thin film evaporator at 155C and a reduced pressure of0.45 mm Hg to remove the low boiling fractions.

Yield: 845 g.

b. o-isohexadecyloxybenzoic acid 3.6 l of N sodium hydroxide were cooledto C whereupon 846 g of bromine were added dropwise in about 30 minutes.The mixture was cooled to 5C whereupon 640 g ofo-isohexadecyloxyacetophenone in 4 l of dioxan were added in 1 hour. Theexothermic reaction was kept between 0 and 5C by external cooling withice. The mixture was then stirred for 1 hour at 30C whereupon it wasrefluxed for 90 minutes. The bromoform formed as well as the dioxan wereremoved by evaporation whereupon the mixture was acidified withhydrochloric acid. The oil-layer formed was extracted with methylenechloride and then concentrated after drying. The volatile substanceswere removed by treatment in a thin film evaporator at 195C and areduced pressure of 0.3 mm.

Yield: 400 g of product comprising 90% of free carboxyl groups.

c. o-isohexadecyloxybenzoyl chloride 400 g of the above carboxylic acidwere heated on a boiling water bath for 3 hours together with 280 ml ofthionyl chloride. After removal of the excess of thionyl chloride theresidue was distilled in a rotating film evaporator at 190C and 0.3 mmHg.

Yield: 341 g.

d. o-isohexadecyloxy-benzoyl acetic acid methyl ester 1 237 g of sodiumethyl acetoacetate suspended in 380 ml of methylene chloride weretreated with 267 g of oisohexadecyloxybenzoyl chloride. The mixture wasleft standing overnight at room temperature and then acidified with 525ml of 2N hydrochloric acid. The methylene chloride was separated fromthe mixture whereupon the mixture was washed 3 times with a 5% solutionof sodium chloride. The organic layer was separated and the methylenechloride removed by evaporation. The residual oil was treated with 38 gof sodium methylate in 1300 ml of methanol, refluxed for 1 hour and thenleft standing overnight at room temperature. After removal of themethanol by evaporation, the residue was taken up in methylene chlorideand washed three times with water. The solvent was removed byevaporation yielding 258 g of an oil having a content of activemethylene groups of 95%.

e. Compound 7 46 g of o-isohexadecyloxybenzoylacetic acid methyl esterand 24 g of Z-(p-aminophenyl)-quinazolone were condensed by boiling inml of xylene and ml of dimethyl formamide, the alcohol formed beingremoved from the reaction mixture. After having been cooled, thereaction mixture was poured into 800 ml of acetonitrile.

Yield: 32 g.

Melting point: 141C.

PREPARATION 8: COMPOUND 8 a. B-isooctadecyIoxy-propionitrile g ofisooctadecyl alcohol commercially available from Farbwerke Hoechst A.G.,Frankfurt (M) Hoechst, W. Germany and l g of sodium methylate werestirred whereupon 30 g of freshly distilled acrylonitrile were addeddropwise at 20C. The mixture was kept for 1 hour at 30C, yielding 149 gof an oil comprising at most 1 of alcohol acccording to thin layerchromatography.

b. B-isooctadecyloxy-propylamine 0.46 mole of the above nitrile washydrogenated at 6065C in a solution of absolute ethanol saturated withammonia, using a hydrogen pressure of 1500 psi and 10 g of Raney nickelas catalyst. After 2 hours the theoretical amount of hydrogen was takenup and the catalyst was filtered off. The mixture was concentrated byevaporation and 126 g of an oil having an amine content of 96% wasobtained. No secondary amine was present.

0. Compound 8 60 g of l-hydroxy-4chloronaphthoic acid phenyl ester and66 g of B-isooctadecyloxypropylamine were heated for 1 hour on an oilbath of 150C. The mixture was then heated under reduced pressure and thephenol formed removed by distillation. The oil formed was boiled twicewith 280 ml of acetonitrile and the oil that separated, after coolingwas isolated. According to thin layer chromatography no amine waspresent anymore.

PREPARATION 9: COMPOUND 9 a. 1-p-methylsulphonylphenyl-3-oisohexadecyloxyphenyl-2-pyrazolin-5-one I 42 g ofo-isohexadecyloxybenzoylacetic acid methyl ester and 19 g ofp-methylsulphonylphenylhydrazine were refluxed for 2 hours in 100 ml ofacetic acid. The acetic acid was removed in a rotating film evaporatorand the residue was treated with decolourizing carbon. The product wasrecrystallized from ml of methanol.

50 Yield: 20 g.

Melting point: 95C.

b. Compound 9 4.7 g of diazotised p-anisidine were added to 16.7 g ofthe above pyrazolin-S -one compound dissolved in 30 55 ml of 2N sodiumhydroxide and 15 ml of ethylene gly- 60 Melting point: 85C.

5 naphtho[ l,2-d]triazole PREPARATION l0: COMPOUND 10 2.9 of2-(2-amino-4-methoxyphenyl)-2I-I- and 3.8 g of pisohexadecyloxybenzoylchloride in 30 ml of dioxan and 0.8 ml of pyridine were heated for 4hours at 60C.

The mixture was poured into water and the oily precipitate was extractedwith chloroform. After washing with water and drying, 6.3 g of residuewere obtained, which after treatment with acetonitrile yielded g ofproduct having a melting point of 80C.

PREPARATION 1 1: COMPOUND 1 1 a. Isohexadecylamine 1 kg ofisohexadecylbromide and 2 litres of liquid ammonia were agitated in anautoclave for 24 hours at 60C. The residue was then treated with 4litres of 40percent acetic acid. Two layers formed and the aqueous layerwas separated and treated with N sodium hydroxide. The oil formed wasextracted with isopropylether, concentrated by evaporation and distilledunder reduced pressure.

Boiling Point: 108C/8 mm.

b. Compound 11 60 g of l-hydroxy-4-chloronaphthoic acid phenyl ester and48.2 g of isohexadecylamine were heated for 1 hour on an oil bath of140C under a reduced pressure of 1 mm. The phenol formed was removed bydistillation and the residue was boiled twice with acetonitr'ile. Theoil layer formed was separated from the layer of acetonitrile.Acccording to thin layer chromatography neither phenol nor startingproducts were present anymore.

PREPARATION 12: COMPOUND 12 a. isooctadecylsulphonylhydrazide A solutionof 36 g of isooctadecylsulphochloride (obtained by treatment of sodiumisooctadecyl sulphonate prepared as described in United Kingdom PatentApplication No. 27,080/70 with thionylchloride) in 80 ml of dioxan wasadded dropwise at room temperature to 25 ml of hydrazine hydrate in 25ml of dioxan. The mixture was stirred for 15 min. and then poured intoicewater. After extraction with methylene chloride and concentration byevaporation, 35 g of oil having a sulphonylhydrazide content of 95% wereobtained.

b. Compound 12 38 g of2-chloro-N-piperidyl-s-carboxymethyl-benzoisothioamide corresponding tothe formula:

[ CHi-CH:

and 35 g of isooctadecylsulphonylhydrazide were heated for 12 hours in300 ml of pyridine at 80C.

The mixture was poured into water and the sticky precipitate wasextracted with methylene chloride whereupon it was washed with 1Nhydrochloric acid and then with water until neutral. The residue wasdried over magnesium chloride and concentrated by evaporation.

Yield: 47 g of an oil having a content of 96% of active mask formingcompound.

The compounds of the invention are preferably incorporated intohydrophilic colloid media from solutions in high-boiling sparinglywater-miscible solvents such as di-n-butyl phthalate and tricresylphosphate or in low-boiling sparingly water-miscible solvents such asethyl acetate, methylene chloride, chloroform, etc. or mixtures thereofin that they have a high solubility therein and very fine dispersionsinhydrophilic colloid compositions of the compounds of the invention canbe obtained by means of these solvents. For this purpose these solutionsare dispersed in extremely fine droplets, preferably in the presence ofa wetting or dispersing agent into the hydrophilic colloid medium thelowboiling sparingly water-miscible solvent then being removed byevaporation.

Of course, the compounds of the invention can also be incorporatedinto,the hydrophilic colloid composition in other ways. For instance,when the compound can be liquefied by slight heating (when it has a lowmelting point) or when it. is liquid at room temperature the liquid canbe dispersed as such in the hydrophilic colloid composition. 1

The hydrophilic colloid composition into which the compounds of theinvention are dispersed need not necessarily be the coating compositionitself of the hydrophilic colloid layer such as a silver halide emulsionlayer into which the compounds are intended to be present. Especially inthe case of photographic emulsion components that are intended to beincorporated into light-sensitive silver halide emulsions, it may beadvantageous to first disperse the components into nonlight-sensitivehydrophilic colloid compositions which are then in their turn admixedwith the colloid coating composition, such as a silver halide emulsion,from which the hydrophilic colloid layer will be coated.

For more details about suitable dispersing techniques that may beemployed for incorporating the compounds of the invention into ahydrophilic colloid layer of a photographic material there can bereferred to e.g. US. Pat. Nos. 2,269,158, 2,284,887, 2,304,939,2,304,940 and 2,322,027, United Kingdom Patent Specification No.791,219, French Patent Specification No. 1,555,663, German PatentSpecification No. 1,127,714 and to Belgian Patent Specification No.747,589.

Since the components containing branched-chain diffusion-fast makinggroups in accordancewith the invention have a higher solubility in thehigh-boiling or low-boiling water-immiscible solvents or mixturesthereof than the corresponding. components with straight-chaindiffusion-fast making groups a larger amount of component can bedispersed in the hydrophilic colloid which is of particular importancein the case of colour couplers since the coupling activity is increasedwhich favours the dye density obtained. The colour couplers yield dyesof excellent stability and spectral characteristics.

By the increased solubility in sparingly watermiscible organic solventsof the components of the invention they have a high reistance tocrystallization. Further, as compared with the corresponding componentshaving a straight-chain diffusion-fast making group the componentsaccording to the invention generally have a lower melting point and someof them are even liquid at room temperature.

In the following table the solubility in ethyl acetate is given inpercentages by weight measured at 40C, of colour couplers according tothe present invention having a branched-chain diffusion-fast makinggroup as defined above, as compared with structurally isomeric colourcouplers having instead of the branched-chain diffusion-fast makinggroup a straight-chain diffusionfast making group with the same numberof carbon atoms.

Table Compound Solubility of the com- Solubility of the strof the poundof the invention ucturally isomeric invention compound 1n thestructurally isomeric colour coupler the hexudecylsulphonyl group is ustraight-chain group but the octyl group in the lposition of theLpyruzolin-S-one ring is still a branched-chain group.

Although the hydrophilic colloid media in which the compounds accordingto the invention are incorporated usually comprise gelatin ashydrophilic colloid, other water-soluble colloidal materials or mixturesof them can be used too e.g. colloidal albumin, zein, casein, acellulose derivative such as carboxyrnethyl cellulose, a synthetichydrophilic colloid such as polyvinyl alcohol, poly-N-vinyl pyrrolidone,etc.

The compounds of the invention may be used in photographic materialscomprising various kinds of photographic emulsion layers. Various silversalts may be used as the sensitive salt such as silver bromide, silveriodide, silver chloride and mixed silver halides such as silverchlorobromide, silver bromoiodide and silver chlorobromoiodide.

The light-sensitive silver halide emulsions may be chemically as well asoptically sensitized. They may be chemically sensitized by effecting theripening in the presence of small amounts of sulphur containingcompounds such as allyl thiocyanate, allyl thiourea, sodiumthiosulphate, etc. The emulsions may also be sensitized by means ofreductors for instance tin compounds as described in French PatentSpecification No. 1,146,955 and in Belgian Patent Specification No.568,687, imino-amino methane sulphinic acid compounds as described inUnited Kingdom Patent Specification No. 789,823 and small amounts ofnoble metal compounds such as gold, platinum, palladium, iridium,ruthenium and rhodium compounds. They may be optically sensitized bymeans of cyanine and merocyanine dyes.

The said emulsions may also comprise compounds which sensitize theemulsions by development acceleration for example compounds of thepolyoxyalkylene type such as alkylene oxide condensation products asdescribed among others in US. Pat. Nos. 2,531,832, 2,533,990, 3,210,191and 3,158,484, in United Kingdom Patent Specification Nos. 920,637 and991,608 and in Belgian Patent Specification No. 648,710 and oniumderivatives of amino-N-oxides as described in United Kingdom PatentSpecification No. 1,121,696.

Further, the emulsions may comprise stabilizers, e. g. heterocyclicnitrogen-containing thioxo-compounds such as benzothiazoline-2-thioneand l-phenyl-Z-tetrazoline-S-thione and compounds of thehydroxytriazolopyrimidine type. They can also be stabilized with mercurycompounds such as the mercury compounds described in Belgian PatentSpecification Nos. 524,121, 677,337 and 707,386 and in US. Pat. No.3,179,520.

The light-sensitive emulsions may also comprise all other kinds ofingredients such as plasticizers, hardening agents, wetting agents, etc.

The emulsions can be coated on a wide variety of photographic emulsionsupports. Typical supports include cellulose ester film, polyvinylacetalfilm, polystyrene film, polyethylene terephthalate film and relatedfilms of resinous materials, as well as paper and glass.

The following examples illustrate the use of the compounds according tothe present invention.

EXAMPLE 1 2 g of compound 1 were dissolved in 6 ml of ethyl acetate. Thesolution was added to 30 ml of a 7% aqueous gelatin solution comprising0.1 g of sodium dodecylbenzenesulphonate whereupon the whole was mixedfor 15 min. by means of a homogenizer.

The ethyl acetate was removed from the colloid composition byevaporation in a rotating film evaporator and then the composition wasadmixed with g of green-sensitized light-sensitive emulsion comprising 5g of silver bromide and 6 g of gelatin. The colour emulsion thus formedwas coated on a support and dried.

After exposure, colour development using N,N-diethyl-p phenylene diaminesulphate as colour developing agent, a treatment in a bleach bath andfixing bath a magenta image was obtained having an absorption maximum of536 nm.

EXAMPLE 2 10 g of compound 6 were dissolved in 30 ml of ethyl acetateand the solution formed was dispersed by means of a homogenizer into 100ml of water comprising 12.5 ml of a 10% aqueous solution ofN-methyloleyltauride sodium salt.

The ethyl acetate was removed from the aqueous composition byevaporation under reduced pressure at 55C and 200-400 mm Hg. In this waya stable dispersion in water of compound 6 was formed.

The aqueous dispersion was then admixed with a conventionalblue-sensitive silver halide emulsion.

We claim:

1. Photographic material comprising a support, a light-sensitive silverhalide emulsion layer on said support and a photographic water-insolublecomponent wherein said component is rendered fast to diffusion inhydrophilic colloid media by the presence in its molecule of a groupcorresponding to the formula:

wherein:

X represents an ether group, a thioether group, a sulphonyl group, aCONl-l group, an NHCO group, or an SO NH group, and

each of R, and R represents a branched-chain C,-C, alkyl group.

2. A photographic material according to claim 1,

wherein R, is a branched-chain C -alkyl group and R is a branched-chainC,,-alkyl group.

3. A photographic material according to claim 1, wherein R, is abranched-chain C,-alkyl group and R is a branched-chain C,, alkyl group.

4. A photographic material according to claim 1, wherein said componentis a cyan-forming colour coupler of the phenol or naphthol type.

wherein:

X represents an ether group, a thioether group, a sulphonyl group, aCONl-l'group, an NHCO group or a SO NH group, and

each of R and R- represents a branched-chain C C alkyl group.

10. A photographic water-insoluble component according to claim 9,wherein R is a branched-chain C alkyl group and R is a branched-chain C-alkyl group.

11. A photographic water-insoluble component according to claim 9,wherein R is a branched-chain C alkyl group and R is a branched-chain C-alkyl group.

12. The photographic material according to claim 1 wherein said group isbonded to Q wherein Q is the residue of a photographic component to beincorporated in a photographic hydrophilic colloid medium in a form fastto diffusion.

1. PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT, A LIGHT-SENSITIVE SILVERHALIDE EMULSION LAYER ON SAID SUPPORT AND A PHOTOGRAPHIC WATER-INSOLUBLECOMPONENT WHEREIN SAID COMPONENT IS RENDERED FAST TO DIFFUSION INHYDROPHILLIC COLLOID MEDIA BY THE PRESENCE IN ITS MOLECULE OF GROUPCORRESPONDING TO THE FORMULA:
 2. A photographic material according toclaim 1, wherein R1 is a branched-chain C8-alkyl group and R2 is abranched-chain C6-alkyl group.
 3. A photographic material according toclaim 1, wherein R1 is a branched-chain C7-alkyl group and R2 is abranched-chain C9 alkyl group.
 4. A photographic material according toclaim 1, wherein said component is a cyan-forming colour coupler of thephenol or naphthol type.
 5. A photographic material according to claim1, wherein said component is a magenta-forming colour coupler of thepyrazolon-or indazolon type.
 6. A photographic material according toclaim 1, wherein said component is a yellow-forming colour coupler ofthe acylacetamide type.
 7. A photographic material according to claim 1,wherein said component is a mask-forming compound.
 8. A photographicmaterial according to claim 1, wherein said component is aU.V.-absorbing compound.
 9. A photographic water-insoluble componentcomprising a group corresponding to the formula:
 10. A photographicwater-insoluble component according to claim 9, wherein R1 is abranched-chain C8-alkyl group and R2 is a branched-chain C6-alkyl group.11. A photographic water-insoluble component according to claim 9,wherein R1 is a branched-chain C7-alkyl group and R2 is a branched-chainC9-alkyl group.
 12. The photographic material according to claim 1wherein said group